CN110452094A - Method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol - Google Patents
Method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol Download PDFInfo
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- CN110452094A CN110452094A CN201910506494.3A CN201910506494A CN110452094A CN 110452094 A CN110452094 A CN 110452094A CN 201910506494 A CN201910506494 A CN 201910506494A CN 110452094 A CN110452094 A CN 110452094A
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- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The invention belongs to the field of preparation of fine chemical intermediate 2,4-dichlorophenol, and particularly relates to a method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol. The method takes phenol and chlorine as raw materials and adds Fe powder or FeCl3Adding p-toluene thiophenol or o-amino thiophenol or phenothiazine as a catalyst promoter into the catalyst, and chlorinating the phenol to prepare the 2,4-dichlorophenol, wherein the method has the advantages of simple operation, high phenol conversion rate of 100 percent and high yield, and can be directly used as a raw material of a 2,4-D raw drug, and in addition, the by-product 2, 6-dichlorophenol, 2,4, 6-trichlorophenol and other impurities have low content.
Description
Technical field
The invention belongs to fine-chemical intermediate 2,4 dichloro phenol preparation fields, are specifically related to a kind of phenol catalytic chlorination
The method for preparing 2,4 dichloro phenol.
Background technique
2,4- chlorophenesic acids, English name are as follows: 2,4-Dichlorophenol, it is synthetic pesticide nitrofen, 2,4-D, poison gram
It dissipates, she is than phosphorus, the medical intermediates such as bithionol and mould inhibitor TCS.Its structural formula is as follows:
The yield of 2, the 4- chlorophenesic acid of traditional phenol catalytic chlorination process production is no more than 90%, and cannot be directly used to give birth to
It produces, impurity 2 therein, 6- chlorophenesic acid can not be separated because physical property is close with 2,4- chlorophenesic acid.With medicine and agriculture
Medicine industry is to high-purity 2, and the demand of 4- chlorophenesic acid, there is an urgent need to be synthetically prepared high-purity 2,4- chlorophenesic acid.
In existing technology, Wang Youping (2,4- chlorophenesic acid new technique for synthesizing [J] science and technology wind, 2012, (17): 29)
Use dichloroethanes as solvent, using phenol as raw material, sulfonic acid chloride is slowly added dropwise at low temperature and carries out selective chlorination, obtains
97% 2,4- chlorophenesic acid crude product obtains 2,4- chlorophenesic acid finished product using precipitation and rectifying.
Sun Changjun etc. (the selective chlorination method synthesis Henan 2,4 dichloro phenol [J] chemical industry, volume 1990,7 (11): 19-
21) use o-chlorphenol as raw material, using aluminum trichloride (anhydrous) and diphenyl sulfide as catalyst, sulfonic acid chloride is used as chlorination
Agent is synthetically prepared 2,4- chlorophenesic acid, and for 2, the 4- chlorophenesic acid purity of synthesis 95% or more, which makees chlorinating agent with sulfonic acid chloride.
Process above is there are some disadvantages, the first technique uses methylene chloride as solvent, and processing is complicated, higher cost.
2,4- chlorophenesic acid purity obtained by second of technique only 95%, cannot be directly used to the production of 2,4-D etc. if do not purified, and
And use o-chlorphenol raw material and sulfonic acid chloride as chlorinating agent, increase production cost.
Summary of the invention
For prior art problem, the present invention provides a kind of method that phenol catalytic chlorination prepares 2,4 dichloro phenol,
For this method with phenol, chlorine is raw material, and Fe powder or FeCl is added3For catalyst, toluene-ω-thiol or near amino thiophenols are added
Or phenthazine, as co-catalyst, 2,4- chlorophenesic acid is made through chlorination in phenol, and this method phenol conversion easy to operate is
100%, high income, and can be directly as the raw material of 2,4-D raw medicine, in addition, by-product 2,6- chlorophenesic acid, 2,4,6- trichloro-benzenes
The impurity contents such as phenol are low.
In order to achieve the above objectives, the technical scheme adopted by the invention is as follows:
A kind of method of phenol catalytic chlorination preparation 2,4- chlorophenesic acid, using phenol as reaction raw materials, with Fe powder or FeCl3As
Co-catalyst is added in catalyst in system, is finally passed through chlorine at 60-65 DEG C, reacts to obtain 2,4- chlorophenesic acid.
It is that the co-catalyst is a kind of in toluene-ω-thiol, near amino thiophenols or phenthazine as improved.
The method of above-mentioned phenol catalytic chlorination preparation 2,4- chlorophenesic acid, comprising the following steps:
Step 1, phenol is added in reaction vessel, and is added with Fe powder or FeCl3It is added as catalyst, while in system
Co-catalyst, warming while stirring is to 60-65 DEG C；
Step 2, the chlorine of 2.0-2.2 times of phenol molal quantity is passed through in 5-6 hours, carries out chlorination reaction；
Step 3, cooling, stop stirring, negates the mixture that should be obtained, and carry out gas chromatographic detection.
Preferably, Fe powder or FeCl3Dosage as catalyst accounts for the 0.3-0.5% of raw material phenol molar fraction.
Preferably, the dosage of co-catalyst accounts for the 0.3-0.5% of raw material phenol molar fraction.
Preferably, the molar ratio of raw material phenol and chlorine is 1:(2.0-2.2).
The utility model has the advantages that
Compared with prior art, for this method with phenol, chlorine is raw material, and Fe powder or FeCl is added3For catalyst, it is added to toluene
As co-catalyst, 2,4- chlorophenesic acid, this method operation is made through chlorination in phenol for thiophenol or near amino thiophenols or phenthazine
Easy phenol conversion is 100%, high income, and can be directly as the raw material of 2,4-D raw medicine, in addition, by-product 2,6- dichloro
Phenol, the impurity contents such as 2,4,6- trichlorophenol, 2,4,6,-Ts are low.
Detailed description of the invention
Fig. 1 is the gas phase map situation of system during phenol chlorination reaction carries out.
Specific embodiment
The invention will be further described combined with specific embodiments below.
Embodiment 1
30.000g phenol is weighed, while 0.054gFe powder is added as catalyst into the system, while 0.119g is added to first
Benzenethiol is as co-catalyst, under conditions of 65 DEG C of reaction temperatures and stirring, thereto with 2.91L/m3-3.54L/m3's
Rate is passed through 6h chlorine and carries out chlorination reaction.Gas-chromatography test, test result such as Fig. 1 institute are carried out to ongoing system is reacted
Show,
| Serial number | Retention time, min | Ingredient names |
| 1 | 13.837 | 2- chlorophenol |
| 2 | 17.778 | Phenol |
| 3 | 21.724 | 2,4- chlorophenesic acids |
| 4 | 35.387 | 4- chlorophenol |
When * carrying out gas chromatographic detection every time, the retention time of each component has the deviation of very little
Phenol chlorizate carries out vapor detection after dilution with toluene, under the same conditions to pure toluene, 2- chlorophenol, phenol,
2,4- chlorophenesic acids, 4- chlorophenol carry out vapor detection, determine each substance retention time table as above, retention time is in 4.0min
Place is toluene, is not considered herein.
After reaction, GC testing result is illustrated in fig. 1 shown below, and retention time is retarder thinner toluene, In 4.0 or so
This is not discussed, and is 2,4- chlorophenesic acid at retention time 21.733min according to illustrating before.Normalization method according to area, 2,
The content of 4- chlorophenesic acid is 97.6%.
| Serial number | Retention time, min | Ingredient names | Content, % |
| 1 | 14.028 | 2- chlorophenol | 2.4 |
| 2 | 21.733 | 2,4- chlorophenesic acids | 97.6 |
Embodiment 2
Except co-catalyst is changed to 0.120g near amino thiophenols, remaining is the same as embodiment 1；Vapor detection reaction mixture, 2,4 ,-
Chlorophenesic acid content 97.2%.
Embodiment 3
Except co-catalyst is changed to 0.191g phenthazine, remaining is the same as embodiment 1；Vapor detection reaction mixture, 2,4 ,-dichloro-benzenes
Phenol content 97.8%.
Embodiment 1-3 examines the influence to this method, as can be seen from the results, with Fe by changing co-catalyst
When powder is catalyst, using phenthazine as the better effect of co-catalyst.
Embodiment 4
30.000g phenol is weighed, while 0.155g FeCl being added into the system3As catalyst, while being added 0.119g pairs
Thiocresol is as co-catalyst, under conditions of 65 DEG C of reaction temperatures and stirring, thereto with 2.91L/m3-3.54L/m3
Rate be passed through 6h chlorine carry out chlorination reaction.Vapor detection reaction mixture, 2,4- chlorophenesic acid contents 97.4%.
Embodiment 5
Except co-catalyst is changed to 0.120g near amino thiophenols, remaining is the same as embodiment 4；Vapor detection reaction mixture, 2,4 ,-
Chlorophenesic acid content 97.6%.
Embodiment 6
Except co-catalyst is changed to 0.191g phenthazine, remaining is the same as embodiment 4；Vapor detection reaction mixture, 2,4 ,-dichloro-benzenes
Phenol content 97.9%.
Embodiment 4-6 examines influence to this method by changing co-catalyst, as can be seen from the results, with
FeCl3When for catalyst, using phenthazine as the better effect of co-catalyst.
Comparative example 1
Weigh 30.000g phenol, while into the system 0.054gFe powder be added as catalyst, in 65 DEG C of reaction temperatures and
Under conditions of stirring, it is passed through chlorine thereto, according to vapor detection as a result, when 2,4- chlorophenesic acid content 43% begins with
The appearance of 2,4,6- trichlorophenol, 2,4,6,-Ts, with continuing for reaction, the content of 2,4,6- trichlorophenol, 2,4,6,-Ts is gradually increased, 2,4- dichloros
The content of phenol is gradually reduced.
Comparative example 2
30.000g phenol is weighed, while 0.155gFeCl is added into the system3As catalyst, 65 DEG C of reaction temperatures with
And under conditions of stirring, it is passed through chlorine thereto, according to vapor detection as a result, when 2,4- chlorophenesic acid content 35% begins with
The appearance of 2,4,6- trichlorophenol, 2,4,6,-Ts, with continuing for reaction, the content of 2,4,6- trichlorophenol, 2,4,6,-Ts is gradually increased, 2,4- dichloros
The content of phenol is gradually reduced.
Two above comparative example shows under conditions of not adding co-catalyst, Fe and FeCl3As catalyst Pyrogentisinic Acid
Conversion ratio there is no reducing, but there are many by-products, the selectivity of 2,4- chlorophenesic acids is not high, with embodiment pair
Than being added after co-catalyst, reaction is obviously improved the selectivity of 2,4- chlorophenesic acid, and by-products content obviously drops
It is low.
It above are only the preferred embodiment of the present invention, there is no need and unable to illustrate to all embodiments.For
For those skilled in the art, without departing from the principle of the present invention, it can also make other various forms of
Variation changes, these also should belong to protection scope of the present invention.
Claims (6)
1. a kind of method of phenol catalytic chlorination preparation 2,4- chlorophenesic acid, which is characterized in that using phenol as reaction raw materials, with Fe
Powder or FeCl3As catalyst, co-catalyst is added in system, is finally passed through chlorine at 60-65 DEG C, reacts to obtain 2,4- bis-
Chlorophenol.
2. a kind of method of phenol catalytic chlorination preparation 2,4- chlorophenesic acid according to claim 1, which is characterized in that described
Co-catalyst is a kind of in toluene-ω-thiol, near amino thiophenols or phenthazine.
3. the method for phenol catalytic chlorination according to claim 1 preparation 2,4- chlorophenesic acid, which is characterized in that including with
Lower step: step 1, phenol is added in reaction vessel, and be added with Fe powder or FeCl3As catalyst, while in system
Co-catalyst is added, warming while stirring is to 60-65 DEG C；Step 2, by 2.0-2.2 times of phenol molal quantity in 5-6 hours
Chlorine is passed through, and carries out chlorination reaction；Step 3, cooling, stop stirring, negates the mixture that should be obtained, and carry out gas-chromatography inspection
It surveys.
4. the method for phenol catalytic chlorination according to claim 3 preparation 2,4- chlorophenesic acid, which is characterized in that including with
Lower step: Fe powder or FeCl3Dosage as catalyst accounts for the 0.3-0.5% of raw material phenol molar fraction.
5. the method for phenol catalytic chlorination according to claim 3 preparation 2,4- chlorophenesic acid, which is characterized in that including with
Lower step: the dosage of co-catalyst accounts for the 0.3-0.5% of raw material phenol molar fraction.
6. the method for phenol catalytic chlorination according to claim 3 preparation 2,4- chlorophenesic acid, which is characterized in that including with
Lower step: the molar ratio of raw material phenol and chlorine is 1:2.0-2.2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724720A (en) * | 2022-11-23 | 2023-03-03 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol micro-channel continuous synthesis process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4160114A (en) * | 1977-07-20 | 1979-07-03 | Reichhold Chemicals, Inc. | Co-catalytic method for obtaining improved chlorination of phenols |
| CN102197010A (en) * | 2008-10-24 | 2011-09-21 | 东曹株式会社 | Process for producing p-dichlorobenzene |
| CN103435453A (en) * | 2013-08-26 | 2013-12-11 | 东南大学 | Method for preparing 2,4-dichlorophenol through directional catalyzing and chlorination of phenol |
| CN106883103A (en) * | 2017-04-25 | 2017-06-23 | 江西天宇化工有限公司 | A kind of preparation method of 2,4 chlorophenesic acid |
-
2019
- 2019-06-12 CN CN201910506494.3A patent/CN110452094B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4160114A (en) * | 1977-07-20 | 1979-07-03 | Reichhold Chemicals, Inc. | Co-catalytic method for obtaining improved chlorination of phenols |
| CN102197010A (en) * | 2008-10-24 | 2011-09-21 | 东曹株式会社 | Process for producing p-dichlorobenzene |
| CN103435453A (en) * | 2013-08-26 | 2013-12-11 | 东南大学 | Method for preparing 2,4-dichlorophenol through directional catalyzing and chlorination of phenol |
| CN106883103A (en) * | 2017-04-25 | 2017-06-23 | 江西天宇化工有限公司 | A kind of preparation method of 2,4 chlorophenesic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115724720A (en) * | 2022-11-23 | 2023-03-03 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol micro-channel continuous synthesis process |
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